CN1201027A - Telchnology for synthesizing 2-amyl-3-butoxy cyclopent-2-enone - Google Patents
Telchnology for synthesizing 2-amyl-3-butoxy cyclopent-2-enone Download PDFInfo
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- CN1201027A CN1201027A CN 97112304 CN97112304A CN1201027A CN 1201027 A CN1201027 A CN 1201027A CN 97112304 CN97112304 CN 97112304 CN 97112304 A CN97112304 A CN 97112304A CN 1201027 A CN1201027 A CN 1201027A
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- amyl group
- reaction
- ketenes
- ring penta
- butoxy
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Abstract
The present invention provides a new technological process for synthesizing 2-amyl-3-butoxycyclopento-2-ketene. Said technological process includes the following steps: cyclizing beta-heptanoyl ethyl propionate into 2-amyl-1,3-cyclopentadiket one under the basic condition, then makingone react with n-butanol to obtain the invented product. As compared with existent technology, said invention can raise reaction yield, its reaction condition is moderate, can reduce toxicity and hazard of its production, and said product can be used as intermediate for synthesizing dihydrojasmone acid methyl ester.
Description
The present invention relates to the novel process of Synthetic 2-amyl group-3-butoxy ring penta-2-ketenes, particularly in solvent, react by β-oenanthyl ethyl propionate (I) and sodium methylate, recrystallization obtains 2-amyl group-1,3-cyclopentanedione (II) (II) reacts the novel process that obtains 2-amyl group-3-butoxy ring penta-2-ketenes (III) with propyl carbinol again under Catalyzed by p-Toluenesulfonic Acid.
In known references, (U.S.Patent 3,671,589) are disclosed to be: carry out Fu-Ke reaction, Synthetic 2-alkyl-1,3-cyclopentanedione by succinyl oxide in the presence of aluminum chloride.
M.F.Ansell and J.W.Ducker[J.Chem.Soc, (London), 1995,329-331] disclosedly be: ring penta-2-ketenes carries out etherification reaction with benzene as solvent with alcohol under P-TsOH catalysis, obtain corresponding alkenone ethers.
Zhou Jingyao (organic chemistry, 1985,6,490-493) disclosedly be: 2-amyl group-1,3-cyclopentanedione and methyl alcohol back flow reaction 1.5 hours under Catalyzed by p-Toluenesulfonic Acid prepares the method for 3-methoxyl group-2-amyl group-ring penta-2-ketenes.
The objective of the invention is for a kind of transformation efficiency height is provided, toxicity is little, easy handling, the novel process of being come Synthetic 2-amyl group-3-butoxy ring penta-2-ketenes by acetoacetic ester in β-oenanthyl through cyclisation, etherificate two-step reaction.
The present invention mainly comprises two big contents, and the temperature of reaction that first control is higher makes β-oenanthyl ethyl propionate can be converted into 2-amyl group-1,3-cyclopentanedione smoothly.Its principles of chemistry are as follows:
R＝CH
3，C
2H
5
It two is the 2-amyl groups-1 that will obtain by above-mentioned reaction, and 3-cyclopentanedione and middle carbon alcohol (propyl carbinol, Pentyl alcohol, n-hexyl alcohol) carry out etherification reaction, obtain 2-amyl group-3-butoxy ring penta-2-ketenes.Its principles of chemistry are as follows:
R '=C
4H
9, C
5H
11, C
6H
13Detailed process is such:
(1) Synthetic 2-amyl group-1, the 3-cyclopentanedione:
Sodium Metal 99.5 divided add in the anhydrous methanol for several times, treat that sodium Metal 99.5 all after the dissolving, is added drop-wise to this solution in the dry xylene gradually.Heat up, β-oenanthyl ethyl propionate is added drop-wise in the reaction system gradually, reaction is carried out under normal pressure, and temperature of reaction is 130-140 ℃, and the best is 135-140 ℃.In order to keep higher temperature of reaction, on reactor, install a fractional column (playing the effect of rectifying tower) additional, reaction be both parallel distillation operation, make lower boiling ethanol distillate system smoothly, high boiling solvent xylene is back to be kept reaction and normally carries out in the system.Fractional column length is to be equivalent to 3 blocks of column plates for well.Reaction times is 1-4 hour, and the best is 2-3 hour.Material proportion is a methyl alcohol: dimethylbenzene: β-oenanthyl ethyl propionate=2-3: 5-10: 1 (m1: ml: g).Add water after reaction finishes and stir, divide and remove organic layer, to system pH＜3, the best is pH=2 to water layer, obtains the beige solid with 10% hcl acidifying, with chloroform-sherwood oil (1: 1 volume ratio) recrystallization, obtains beige needle crystal solid.
(3) Synthetic 2-amyl group-3-butoxy ring penta-2-ketenes: with 2-amyl group-1,3-cyclopentanedione, propyl carbinol and catalyzer tosic acid together add and carry out back flow reaction in the reactor.Proportioning raw materials is a 2-amyl group-1, the 3-cyclopentanedione: propyl carbinol=1: 3-10 (mol ratio) is preferably 1: 4-6 (mol ratio).Propyl carbinol also can be a Pentyl alcohol, n-hexyl alcohol, preferably propyl carbinol.The tosic acid consumption is 25-40%, be preferably 30-33% (with 2-amyl group-1, the 3-cyclopentanedione is a benchmark, wt%), preferably 33%.Reaction can be carried out under decompression (50-80KPa) or normal pressure, and its temperature is a reflux temperature.Reaction times continues reaction and can finish reaction in 1.5-3 hour by going out the water speed decision after anhydrous telling.
Sodium bicarbonate aqueous solution with 5% and 10% sodium chloride aqueous solution be the washing reaction thing respectively, be washed till neutrality with deionized water again, decompression steams the propyl carbinol into reaction, continue underpressure distillation, obtain 2-amyl group-3-butoxy ring penta-2-ketenes, boiling point 140-141 ℃/133-266Pa, can be used for making each methyl dihydrojasmonate.
The present invention compares with existent method, has obvious superiority, with β-oenanthyl ethyl propionate Synthetic 2-amyl group-1,3-cyclopentanedione: (1), sufficient raw.β-oenanthyl ethyl propionate generates the oenanthyl diethyl succinate by enanthaldehyde and diethyl maleate reaction, obtains after the decarboxylation.The former is the Viscotrol C split product, also is main large byproduct of production engineering plastic nylon-11; (2), temperature of reaction is higher, and reaction is carried out smoothly, can obtain higher productive rate thus; (3), can carry out suitability for industrialized production, have and produce and feasibility economically.Synthetic 2-amyl group-3-butoxy ring penta-2-ketenes: (1), technology are simple, easy and simple to handle, are suitable for carrying out suitability for industrialized production; (2), replace the benzene series noxious solvent, it is harmless that operational path is realized with middle carbon alcohol, CR production, and social benefit is especially remarkable.
Enumerate several embodiments of the present invention below:
Embodiment 1:
Is furnished with agitator at one, in the 1000ml flask of thermometer flavor form fractional column, add the 420ml dry xylene, stir down sodium methoxide solution 14g (0.16mol) sodium Metal 99.5 to be divided and join in the 140ml anhydrous methanol for several times, form sodium methoxide solution after the sodium Metal 99.5 complete reaction) splash into gradually in the dry xylene, heating, steam most of methyl alcohol, temperature is risen to 〉=boils off 139 ℃ the time residual methyl alcohol and part dimethylbenzene, under the stirring that refluxes, slowly splash into 60g (0.28mol) β-oenanthyl ethyl propionate, temperature of charge is not less than 135 ℃ in the dropping process, finish, add dry xylene 200ml (amount of steaming) again, take off flavor form fractional column, ball-type condenser changes the outfit, continued back flow reaction 1.5 hours, 138 ℃ of reflux temperatures.
Reaction finishes postcooling to room temperature, and adding distil water 280ml stirred 30 minutes.This moment, feed liquid was the beige suspension liquid, pH=12.Standing demix is removed oil phase (dimethylbenzene layer), and water to pH=3, obtains the beige solid with 10% hcl acidifying, uses chloroform-sherwood oil (1: 1 volume ratio) recrystallization again, obtains 32.2g beige needle crystal, yield 68.45%, m.p.140-142 ℃.
Embodiment 2:
In three mouthfuls of round-bottomed flasks of the 500ml that has water trap, add 20.2g (0.12mol) 2-amyl group-1,3-cyclopentanedione (embodiment 1 makes), 44.4g (0.6mol) propyl carbinol and 6.1g (0.032mol) tosic acid, induction stirring, oil bath is heated to back flow reaction.Temperature of reaction rises to 126 ℃ gradually by 118 ℃, this moment substantially anhydrous telling, it is orange red that reaction solution is.Be cooled to room temperature, 5% sodium bicarbonate aqueous solution washing with 50ml divides the phase of anhydrating, and 10% sodium chloride solution with 50ml is washed till neutrality again, after branch anhydrates mutually, the oil phase distilled water wash adds anhydrous magnesium sulfate drying, filters, underpressure distillation removes and desolvates, continue decompression steam 22.7g product 2-amyl group-3-butoxy ring penta-2-ketenes, yield 84.45%, b.p.147 ℃/133-260Pa.
What narrate above only is the relevant condition that adopts according to qualifications usually in this invention of enforcement, and its meaning is all flexible and adjustment that comprise this invention actual conditions in order to separate.The purpose of selecting these conditions to show here can not depart from the marrow and the scope of claim.
Claims (3)
1, the novel process of a kind of Synthetic 2-amyl group-3-butoxy ring penta-2-ketenes comprises that with β-oenanthyl ethyl propionate (I) be raw material, adds sodium methoxide solution in the dry xylene gradually, boil off methyl alcohol, treat that temperature rises to 138-140 ℃, stir and slowly drip (I) down, maintenance system temperature 〉=130 ℃ in the dropping process, drip and finish, continue to reflux and stirred hydrolysis 2 hours, acidifying, recrystallization obtains 2-amyl group-1,3-cyclopentanedione (II); (II) and propyl carbinol are added in the reactor, in the presence of tosic acid, carry out etherification reaction, reaction finishes the back alkali cleaning, salt is washed, be washed to neutrality, remove and desolvate, underpressure distillation obtains 2-amyl group-3-butoxy ring penta-2-ketenes, temperature 〉=125 ℃ that it is characterized in that cyclization, in the etherification reaction propyl carbinol promptly as reactant again as reaction solvent.
2, the technology of Synthetic 2-amyl group as claimed in claim 1-3-butoxy ring penta-2-ketenes is characterized in that installing fractionation plant on cyclization reactor, assurance cyclization temperature 〉=125 ℃.
3, the novel process of Synthetic 2-amyl group as claimed in claim 1-3-butoxy ring penta-2-ketenes is characterized in that making reaction solvent with propyl carbinol, and solvent load is (II): propyl carbinol=1: 3-10 (mol ratio).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97112304 CN1201027A (en) | 1997-06-04 | 1997-06-04 | Telchnology for synthesizing 2-amyl-3-butoxy cyclopent-2-enone |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97112304 CN1201027A (en) | 1997-06-04 | 1997-06-04 | Telchnology for synthesizing 2-amyl-3-butoxy cyclopent-2-enone |
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| CN1201027A true CN1201027A (en) | 1998-12-09 |
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|---|---|---|---|
| CN 97112304 Pending CN1201027A (en) | 1997-06-04 | 1997-06-04 | Telchnology for synthesizing 2-amyl-3-butoxy cyclopent-2-enone |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7897802B2 (en) | 2005-06-30 | 2011-03-01 | Asahi Kasei Chemicals Corporation | Process for production of substituted cyclopentanone |
| CN105001130A (en) * | 2015-07-07 | 2015-10-28 | 张琳苹 | Synthesis method of 3-aryl-2-cyclopenten-1-one compound |
| CN107226778A (en) * | 2017-06-02 | 2017-10-03 | 天津市安凯特科技发展有限公司 | A kind of synthetic method of dihydro jasmone |
-
1997
- 1997-06-04 CN CN 97112304 patent/CN1201027A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7897802B2 (en) | 2005-06-30 | 2011-03-01 | Asahi Kasei Chemicals Corporation | Process for production of substituted cyclopentanone |
| CN105001130A (en) * | 2015-07-07 | 2015-10-28 | 张琳苹 | Synthesis method of 3-aryl-2-cyclopenten-1-one compound |
| CN105001130B (en) * | 2015-07-07 | 2016-10-05 | 青岛大学附属医院 | A kind of synthetic method of 3-aryl-2-cyclopentene-1-one compound |
| CN107226778A (en) * | 2017-06-02 | 2017-10-03 | 天津市安凯特科技发展有限公司 | A kind of synthetic method of dihydro jasmone |
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